CN103413973A - Preparation method of PAALi-g-SiO2-doped nanofiber-based composite gel polymer electrolyte - Google Patents

Preparation method of PAALi-g-SiO2-doped nanofiber-based composite gel polymer electrolyte Download PDF

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CN103413973A
CN103413973A CN2013102439269A CN201310243926A CN103413973A CN 103413973 A CN103413973 A CN 103413973A CN 2013102439269 A CN2013102439269 A CN 2013102439269A CN 201310243926 A CN201310243926 A CN 201310243926A CN 103413973 A CN103413973 A CN 103413973A
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李为立
邢玉金
杨刚
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Jiangsu University of Science and Technology
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Abstract

The invention discloses a preparation method of PAALi-g-SiO2-doped nanofiber-based composite gel polymer electrolyte which is applied to a polymer lithium-ion battery. The method comprises the following steps of first preparing PAALi-g-SiO2, then mixing the PAALi-g-SiO2 with PVDF (polyvinylidene fluoride) according to a mass ratio of (1:2) to (1:6), then dispersing the mixture into a N'N-dimethylformamide/acetone (3:1) mixed solution, preparing a composite nanofiber polymer film by adopting an electrostatic spinning method, and adsorbing liquid electrolyte with the mass being 100(wt)% to 300(wt)% of that of the film after the film is dried so as to activate the film. The thickness range of the obtained composite nanofiber gel polymer electrolyte is 80micrometers to 100micrometers, the ion conductivity maximally can reach 3.26*10<-3>S cm<-1> at the temperature of 25 DEG C, and an electrochemical window can reach 5.0V. The preparation method has a good prospect in the field such as the polymer lithium-ion battery.

Description

Doping PAALi-g-SiO 2Nanofiber-based plural gel method for preparing polymer electrolytes
Technical field
The present invention relates to a kind of doping PAALi-g-SiO that is applied to polymer Li-ion battery 2Nanofiber-based plural gel method for preparing polymer electrolytes.
Background technology
Gel polymer electrolyte (GPE) is to add liquid plasticizer to be similar to a base polymer electrolyte of gelling properties later, it consists of high molecular polymer, metal lithium salts and plasticizer ternary component, on apparent, be solid-state, but its ion transfer mainly occurs in the liquid phase of gel phase and its absorption, and transporting mechanism is similar to liquid electrolyte.The leakage of liquid electrolyte namely can not occur in GPE, can retain again the characteristic of solid electrolyte, makes it in the application of lithium ion battery, solar cell, fuel cell, capacitor homenergic storage device, be subject to paying close attention to widely.
The material that GPE polymer matrix used is low price, be easy to prepare, as Kynoar (PVDF), polyacrylonitrile (PAN), polymethyl methacrylate (PMMA), poly(ethylene oxide) (PEO), polyvinyl chloride (PVC) etc.As everyone knows, PVDF is a kind of thermoplastic polymer of hemicrystalline, its have good mechanical property, chemical resistance, heat-resisting quantity and, the property such as dielectricity, pyroelectricity etc.Just because of these good performances, make it become the desirable host material of lithium ion battery porous polymer electrolyte.PVDF has following features as porous polymer matrix: (1) good film-forming property is easy to realize batch production; (2) dielectric constant large (ε=8.4), help lend some impetus to the dissolving of lithium salts in polymer; (3) glass transition temperature is high, is conducive to improve the thermal stability of polymer dielectric; (4) strong electron-withdrawing group group-CF makes the PVDF antianode show high chemistry and electrochemical stability.The PVDF of take has immersion precipitation, hot phase separation method, method of electrostatic spinning etc. as matrix prepares porous polymer electrolyte.Wherein, method of electrostatic spinning is the main and the most promising method of producing thin, smooth and uniform polymeric dielectric film.In the electrostatic spinning process, polymer solution or molten mass are forced through electrostatic field by shower nozzle.By method of electrostatic spinning, prepare the average diameter of fiber at 200nm～1 μ m, than extremely when young 10～100 times of the fibre diameters of traditional melt spinning.Therefore, the Static Spinning film has very high specific area and the nanometer unique pore structure to micron level.
As a kind of polymer of hemicrystalline, PVDF has crystalline phase and unformed phase simultaneously.Its crystallized domains has hindered the infiltration of liquid electrolyte and the migration of lithium ion; Therefore, the PVDF of high crystalline becomes one of principal element that reduces the polymer dielectric ionic conductivity.And, still there is the leakage of the electrolyte caused due to being separated between polymeric matrix and Electolyte-absorptive.The loss of electrolyte may further cause loose contact between electrode and electrolyte and the reduction of ionic conductivity.Above all these limited the electrostatic spinning pvdf membrane and applied in lithium ion battery.
Summary of the invention
Based on this, the present invention designs synthetic a kind of modified particle PAALi-g-SiO 2, i.e. Ionomer PAALi grafting coats gas phase SiO 2, by its doping PVDF solution, preparing the composite nano fiber polymer film by method of electrostatic spinning, thin film adsorbs liquid electrolyte swell gel is to obtain nanofiber-based plural gel polymer dielectric.
In order to achieve the above object, the technical scheme taked of the present invention is:
A kind of doping PAALi-g-SiO 2Nanofiber-based plural gel method for preparing polymer electrolytes,
At first prepare PAALi-g-SiO 2: by the specific area scope at 200m 2/ g～400m 2/ g hydrophilic gas phase SiO 2With silane coupler γ-methacryloxypropyl trimethoxy silane in mass ratio 10:1～1:1 mix and be scattered in ethanolic solution, first magnetic agitation 1～2 hour, then ultrasonic dispersion is 1～2 hour, it is 2-5 that dropping hydrochloric acid makes system pH, last 65～85 ℃ of reactions 4～8 hours, obtain surface by sol gel reaction and for γ-methacryloxypropyl trimethoxy silane, coat the SiO of modification 2Dispersion liquid, by dispersion liquid high speed centrifugation, the washing obtained, remove accessory substance 3 times repeatedly, in 100～120 ℃ of vacuum drying ovens, toasts after 12～24 hours and grind, and obtains the SiO that γ-methacryloxypropyl trimethoxy silane coats modification 2Particle; Then by lithium hydroxide (LiOH) and acrylic acid (AA) in molar ratio 1:1 at room temperature react and obtained Lithium acrylate (AALi) in 2～6 hours, itself and γ-methacryloxypropyl trimethoxy silane are coated to the SiO of modification 2Particle 2:1～6:1 mixing in mass ratio is scattered in N, in dinethylformamide (DMF) solution, the solution concentration of mixture is 10～30wt%, after mixing is uniformly dispersed, add AIBN with respect to AALi quality 1～5% as initator, 70～90 ℃ of reactions 5～6 hours.Resulting polymers grafting particle solution is centrifugal, washing, 3 times repeatedly, remove unreacted accessory substance, finally dry, grind, namely obtain the described PAALi-g-SiO of this patent 2.
By molecular weight ranges, be M n=6 * 10 5～1 * 10 6The PVDF powder dissolution in the mixed solution that DMF and acetone form for 3:1 by volume, under room temperature, stir after 12～24 hours and add PAALi-g-SiO 2, it is 1:2～1:6 with the PVDF quality than scope, stirs after 2～3 hours ultrasonic dispersion again and makes it to mix in 6～8 hours, obtaining mixture solution concentration is 0.12g/ml.After polymer solution vacuum degassing bubble, be placed on electrostatic spinning apparatus, the adjusting fltting speed is 1～3ml/h, and electrostatic field voltage is 15～18Kv, and receiving range is 15～20cm, can on collecting board, obtain nanofiber-based composite polymer films after 5～8 hours.
The composite nano fiber thin polymer film obtained is vacuumized to heat drying 8～12 hours at the temperature of 80～100 ℃, again in glove box the immersion liquid electrolyte (liquid electrolyte is that the hexafluoro of 1M concentration closes lithium phosphate and mixes by dimethyl carbonate, the mixed solution that methyl ethyl carbonate and ethylene carbonate form by 1:1:1) 0.5～1 hour, control the adsorbance of liquid electrolyte, making its adsorption rate is with respect to nanofiber-based composite polymer films quality 100%wt～300wt%, to obtain nanofiber-based plural gel polymer dielectric, its thickness range is 80～100 μ m.
Advantage of the present invention and beneficial effect are:
1, PAALi-g-SiO 2With the PVDF blend, be scattered in mixed solvent, by method of electrostatic spinning, prepare the average diameter of composite nano fiber porous membrane fiber at 200nm～1 μ m, than extremely when young 10-100 times of the fibre diameter of traditional melt spinning.Therefore, the Static Spinning film has very high specific area and nanometer to unique pore structure of micron level, is conducive to improve the adsorption rate of its liquid electrolyte, thereby improves the ionic conductivity of nanofiber-based plural gel polymer dielectric.
2, PAALi-g-SiO 2The dissociable lithium ion that goes out can carry out ionic conduction, improve system intermediate ion carrier content, and this also is conducive to improve the cyclical stability in its ionic conductivity and charge and discharge process.
3, PAALi-g-SiO 2Not only had the character of polymer but also retained the activity of part inorganic particulate, by itself and the blend of PVDF matrix can be given full play to the characteristics of blend two-phase, make the nanofiber-based plural gel polymer dielectric of preparation have chemical property and mechanical property preferably.
Its room-temperature ion conductance of nanofiber-based plural gel polymer dielectric of the present invention reaches 10 -3Scm -1The order of magnitude, electrochemical stability window reaches 5.0V, realistic polymer Li-ion battery instructions for use.
The accompanying drawing explanation
Fig. 1 is the flying-spot microscope figure of the nanofiber-based composite polymer films of embodiment 1 preparation;
Fig. 2 is the ac impedance spectroscopy curve chart of nanofiber-based plural gel polymer dielectric under different temperatures of embodiment 1 preparation;
Fig. 3 is the electrochemical stability window result of the nanofiber-based plural gel polymer dielectric of embodiment 1 preparation;
Fig. 4 is that the ionic conductivity of the nanofiber-based plural gel polymer dielectric for preparing of embodiment 1-3 is along with the variations in temperature relation curve;
Fig. 5 is the charge-discharge performance figure of the polymer Li-ion battery based on nanofiber-based plural gel polymer dielectric assembling of embodiment 1 preparation.
Embodiment
Embodiment 1
(1) by the 10g specific area, be 200m 2The gas phase SiO of/g 2With 1g γ-methacryloxypropyl trimethoxy silane, mix and be dissolved in ethanolic solution, first magnetic agitation 2 hours, then ultrasonic dispersion is 2 hours, it is 3 that dropping hydrochloric acid makes system pH, last 75 ℃ of reactions 6 hours, by the collosol and gel dealcoholization, obtaining surface has the SiO that coats modification with γ-methacryloxypropyl trimethoxy silane 2Dispersion liquid, will obtain dispersion liquid high speed centrifugation, washing, repeatedly remove accessory substance 3 times, and in 100 ℃ of vacuum drying ovens, baking is 18 hours, then grinds, and obtains the SiO that γ-methacryloxypropyl trimethoxy silane grafting coats 2Particle.
(2) 24g LiOH was at room temperature reacted 4 hours with 72g acrylic acid (AA), obtain Lithium acrylate (AALi);
(3) SiO resulting γ-methacryloxypropyl trimethoxy silane grafting in 40g Lithium acrylate (AALi) and 10g step (1) coated 2The particle mixing is scattered in DMF solution, and the solution concentration of mixture is 30wt%, after mixing is uniformly dispersed, adds the AIBN of 0.8g as initator, and 80 ℃ were reacted 6 hours.Resulting polymers grafting particle solution is centrifugal, washing, 3 times repeatedly, remove unreacted accessory substance, finally dry, grind, namely obtain PAALi-g-SiO 2.
(4) in 83ml DMF and the acetone mixed solution that 3:1 forms by volume, by the 8g molecular weight be Mn=6 * 105 the PVDF powder dissolution in the inner, under room temperature, stirred 18 hours until be uniformly dissolved, then add 2g PAALi-g-SiO 2Stir after 2 hours ultrasonic dispersion again made it to mix in 7 hours, obtaining mixture solution concentration is 0.12g/ml, after polymer solution vacuum degassing bubble, be placed on electrostatic spinning apparatus, the adjusting fltting speed is 2ml/h, and electrostatic field voltage is 15kV, receiving range is 18cm, can on collecting board, obtain nanofiber-based composite polymer electrolyte film after 7 hours.
(5) nanofiber-based composite polymer films is 100 ℃ vacuumize dry 8 hours, immersion liquid electrolyte 1 hour in glove box again, control the adsorbance of liquid electrolyte, making its adsorption rate is with respect to nanofiber-based composite polymer films quality 300wt%, to obtain final nanofiber-based plural gel polymer electrolyte film, the film thickness prepared is about 90 μ m.Wherein liquid electrolyte is that the hexafluoro of 1M concentration closes lithium phosphate and mixes the mixed solution be comprised of by 1:1:1 dimethyl carbonate, methyl ethyl carbonate and ethylene carbonate.
Fig. 1 is the ESEM picture of the nanofiber-based plural gel electrostrictive polymer degrading film for preparing of embodiment 1.As can be seen from the figure these fibers present tridimensional network, and the higher mechanical strength that this structure can not only be given polymer dielectric film can also form the pore structure of a series of fully interconnected micron-scales, is conducive to the adsorptive liquid electrolyte.
Fig. 2 is sandwiched in the nanofiber-based plural gel electrostrictive polymer degrading film that embodiment 1 prepares between stainless steel electrode, the interchange spectral curve that test obtains under different temperatures.Because what adopt is the stainless steel blocking electrode, there is no electrochemical reaction, the circular arc portion of electrochemical reaction can regard the diameter infinity as so represent in impedance spectrum, shows as in the drawings approximate straight line.According to the crossing point of real axis on Nyquist curve in ac impedance spectroscopy and impedance spectrogram, calculate the resistance R of polymer dielectric b, by σ=l/R bA calculates the ionic conductivity (σ) (wherein, L is film thickness, and A is the area of film) that the composite nano fiber polymer electrolyte film is calculated in examination, and under its room temperature, (25 ℃) ionic conductivity reaches 3.26 * 10 -3S cm -1.
Fig. 3 is that the nanofiber-based plural gel polymer electrolyte film linear sweep voltammetry curve test result at room temperature that embodiment 1 prepares (be take stainless steel as work is anodal, lithium metal is negative pole and reference electrode, during nanofiber-based plural gel polymer electrolyte film is sandwiched in), its electrochemical stability window is 5.0V.
Fig. 5 is that the nanofiber-based plural gel electrostrictive polymer degrading film charge and discharge cycles curve chart that example 1 prepares (is assembled into Li/GPE/LiCoO 2Battery, the 0.1C rate charge-discharge).As can be seen from the figure, with the battery of nanofiber-based plural gel polymer electrolyte film assembling, have higher initial discharge capacity and good cyclical stability.After circulation 50 circles, its discharge capacity still can reach 90.8% of initial discharge capacity, and enclosed pasture efficiency is up to 98.3%.Therefore, the application of nanofiber-based plural gel polymer electrolyte film in polymer Li-ion battery has prospect preferably.
Embodiment 2
(1) by the 5g specific area, be 400m 2The gas phase SiO of/g 2With 1g γ-methacryloxypropyl trimethoxy silane, mix and be dissolved in ethanolic solution, first magnetic agitation 1.5 hours, then ultrasonic dispersion is 1.5 hours, it is 2 that dropping hydrochloric acid makes system pH, last 85 ℃ of reactions 8 hours, by the collosol and gel dealcoholization, obtaining surface has the SiO that coats modification with γ-methacryloxypropyl trimethoxy silane 2Dispersion liquid, will obtain dispersion liquid high speed centrifugation, washing, repeatedly remove accessory substance 3 times, and in 110 ℃ of vacuum drying ovens, baking is 24 hours, then grinds, and obtains the SiO that γ-methacryloxypropyl trimethoxy silane grafting coats 2Particle.
(2) 24g LiOH was at room temperature reacted 2 hours with 72g acrylic acid (AA), obtain Lithium acrylate (AALi);
(3) SiO resulting γ-methacryloxypropyl trimethoxy silane grafting in 20g Lithium acrylate (AALi) and 10g step (1) coated 2The particle mixing is scattered in DMF, and the solution concentration of mixture is 10%, after mixing is uniformly dispersed, adds the AIBN of 0.2g as initator, and 90 ℃ were reacted 5 hours.Resulting polymers grafting particle solution is centrifugal, washing, 3 times repeatedly, remove unreacted accessory substance, finally dry, grind, namely obtain PAALi-g-SiO 2.
(4) at 58ml N, dinethylformamide (DMF) and acetone is the mixed solution of 3:1 composition by volume, by the 6g molecular weight be Mn=8 * 105 the PVDF powder dissolution in the inner, under room temperature, stirred 12 hours until be uniformly dissolved, then add 1g PAALi-g-SiO 2Stir after 2.5 hours ultrasonic dispersion again made it to mix in 6 hours, obtaining mixture solution concentration is 0.12g/ml, after polymer solution vacuum degassing bubble, be placed on electrostatic spinning apparatus, the adjusting fltting speed is 1ml/h, and electrostatic field voltage is 17kV, receiving range is 15cm, can on collecting board, obtain nanofiber-based composite polymer electrolyte film after 8 hours.
(5) nanofiber-based composite polymer films is 90 ℃ vacuumize dry 10 hours, immersion liquid electrolyte 0.8 hour in glove box again, control the adsorbance of liquid electrolyte, making its adsorption rate is with respect to nanofiber-based composite polymer films quality 270wt%, to obtain final nanofiber-based plural gel polymer electrolyte film, the film thickness prepared is about 100 μ m.
Embodiment 3
(1) by the 10g specific area, be 300m 2The gas phase SiO of/g 2With 10g γ-methacryloxypropyl trimethoxy silane, mix and be dissolved in ethanolic solution, first magnetic agitation 1 hour, then ultrasonic dispersion is 1 hour, it is 5 that dropping hydrochloric acid makes system pH, last 65 ℃ of reactions 4 hours, by the collosol and gel dealcoholization, obtaining surface has the SiO that coats modification with γ-methacryloxypropyl trimethoxy silane 2Dispersion liquid, will obtain dispersion liquid high speed centrifugation, washing, repeatedly remove accessory substance 3 times, and in 120 ℃ of vacuum drying ovens, baking is 12 hours, then grinds, and obtains the SiO that γ-methacryloxypropyl trimethoxy silane grafting coats 2Particle.
(2) 24g LiOH was at room temperature reacted 6 hours with 72g acrylic acid (AA), obtain Lithium acrylate (AALi);
(3) by resulting SiO in 60g Lithium acrylate (AALi) and 10g step (1) 2Particle is dissolved in DMF, adds the AIBN of 3g as initator, and 70 ℃ were reacted 5.5 hours.Resulting polymers grafting particle solution is centrifugal, washing, 3 times repeatedly, remove unreacted accessory substance, finally dry, grind, namely obtain PAALi-g-SiO 2.
(4) in 75ml DMF and the acetone mixed solution that 3:1 forms by volume, by the 6g molecular weight be Mn=1 * 106 the PVDF powder dissolution in the inner, under room temperature, stir 24 hours until be uniformly dissolved, then add 3g PAALi-g-SiO2, stir after 3 hours ultrasonic dispersion again made it to mix in 8 hours, obtaining mixture solution concentration is 0.12g/ml, after polymer solution vacuum degassing bubble, be placed on electrostatic spinning apparatus, the adjusting fltting speed is 3ml/h, electrostatic field voltage is 18kV, receiving range is 20cm, after 5 hours, can on collecting board, obtain nanofiber-based composite polymer electrolyte film.
(5) the composite nano fiber thin polymer film is 80 ℃ vacuumize dry 12 hours, immersion liquid electrolyte 0.5 hour in glove box again, control the adsorbance of liquid electrolyte, making its adsorption rate is with respect to nanofiber-based composite polymer films quality 100wt%, to obtain final nanofiber-based plural gel polymer electrolyte film, the film thickness prepared is about 80 μ m.
Fig. 4 is the ionic conductivity variation with temperature situation of the nanofiber-based plural gel polymer dielectric of embodiment 1-3.Its linear relationship shows, the ionic conductivity of this nanofiber-based plural gel polymer electrolyte film varies with temperature consistent with the Arrhenius equation of testing, and meets the universal law of gel polymer electrolyte ionic conduction.Because temperature raises, cause material volume to expand, cause producing more free space, promote the migration of polymer segment and lithium ion.In addition, along with the rising PAALi-g-SiO of temperature 2Thereby also can dissociate the raising that more lithium ion further promotes ionic conductivity.Common this phenomenon can be observed in liquid electrolyte and gel polymer electrolyte.

Claims (4)

  1. One kind the doping PAALi-g-SiO 2Nanofiber-based plural gel method for preparing polymer electrolytes, it is characterized in that comprising the steps:
    Step 1, by gas phase SiO 2With silane coupler γ-methacryloxypropyl trimethoxy silane in mass ratio 10:1～1:1 mix and be scattered in ethanolic solution, first magnetic agitation 1～2 hour, then ultrasonic dispersion is 1～2 hour, it is 2-5 that dropping hydrochloric acid makes system pH, finally the temperature range of 65～85 ℃, reacted 4～8 hours, by the collosol and gel dealcoholization, obtaining surface has the SiO coated with γ-methacryloxypropyl trimethoxy silane grafting 2Dispersion liquid; By dispersion liquid high speed centrifugation, the washing obtained, repeatedly remove accessory substance 3 times, in 100～120 ℃ of vacuum drying ovens, toasted 12～24 hours, then grind, obtain γ-methacryloxypropyl trimethoxy silane grafting coated Si O 2Particle; Then by lithium hydroxide and acrylic acid in molar ratio 1:1 at room temperature react and obtained Lithium acrylate in 2～6 hours, by Lithium acrylate and the γ-methacryloxypropyl trimethoxy silane grafting coated Si O obtained 2Particle 2:1～6:1 in mass ratio is scattered in DMF, and the solution concentration of mixture is 10～30wt%, after mixing and being uniformly dispersed, then adds AIBN with respect to Lithium acrylate quality 2～5%wt% as initator, 70～90 ℃ of reactions 5～6 hours; Resulting polymers grafting particle solution is centrifugal, washing, 3 times repeatedly, remove the accessory substance into reaction, dry, grind, namely obtain PAALi-g-SiO 2Powder;
    Step 2, in the mixed solution that DMF and acetone form for 3:1 by volume, first by the Kynoar powder dissolution in the inner, after under room temperature, stirring 12～24 hours, then the PAALi-g-SiO that adds step 1 to obtain 2Powder, PAALi-g-SiO 2With the Kynoar quality than scope, be 1:2～1:6, obtaining mixture solution concentration is 0.12g/ml, under room temperature, stirs after 2～3 hours ultrasonic dispersion again and makes it to mix in 6～8 hours; By after mixture solution vacuum degassing bubble, be placed on electrostatic spinning apparatus, the adjusting fltting speed is 1ml/h～3ml/h, and electrostatic field voltage is 15～18Kv, receiving range is 15～20cm, can on collecting board, obtain nanofiber-based composite polymer films after 5～8 hours;
    Step 3, the nanofiber-based composite polymer films that step 2 is prepared vacuumize heat drying 8～12 hours at the temperature of 80～100 ℃, immersion liquid electrolyte 0.5～1 hour in glove box again, control the adsorbance of liquid electrolyte, make its adsorption rate for the 100%wt～300wt% with respect to nanofiber-based composite polymer films quality, take and obtain the composite nano fiber gel polymer electrolyte of thickness as 80～100 μ m.
  2. 2. according to the described doping of claim one PAALi-g-SiO 2Nanofiber-based plural gel method for preparing polymer electrolytes, it is characterized in that the described gas phase SiO of step 1 2The specific area scope be 200m 2/ g～400m 2/ g hydrophilic gas phase SiO 2.
  3. 3. doping PAALi-g-SiO according to claim 1 2Nanofiber-based plural gel method for preparing polymer electrolytes, the molecular weight ranges that it is characterized in that the described Kynoar of step 3 is M n=6 * 10 5～1 * 10 6.
  4. 4. doping PAALi-g-SiO according to claim 1 2Nanofiber-based plural gel method for preparing polymer electrolytes, it is characterized in that described liquid electrolyte is that the hexafluoro of 1M concentration closes lithium phosphate and mixes the mixed solution be comprised of by 1:1:1 dimethyl carbonate, methyl ethyl carbonate and ethylene carbonate.
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CN105633475A (en) * 2016-01-12 2016-06-01 齐鲁工业大学 Preparation method of solid polymer electrolyte for lithium ion battery
CN111276695A (en) * 2020-02-17 2020-06-12 电子科技大学 All-solid-state lithium fluorinated carbon secondary battery and preparation method thereof
CN113622053A (en) * 2020-05-08 2021-11-09 上海微创医疗器械（集团）有限公司 Fiber and preparation method thereof, film, covered stent and preparation method thereof
CN114497721A (en) * 2022-01-07 2022-05-13 哈尔滨工业大学 Composite electrolyte film, preparation method thereof and application thereof in solid-state lithium battery
CN114497721B (en) * 2022-01-07 2023-07-21 哈尔滨工业大学 Composite electrolyte film, preparation method thereof and application thereof in solid-state lithium battery

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